Phosphorylated thiourea compositions

ABSTRACT

NEW COMPOUNDS CORRESPONDING TO THE GENERIC FORMULA:   1-(R-P(=X)(-R1)-NH-),2-(R2-CO-NH-C(=S)-NH-)BENZENE   WHEREIN X CAN BE SELECTED FROM OXYGEN AND SULFUR, R AND R1 CAN BE THE SAME OR DIFFERENT AND CAN BE SELECTED FROM LOWER LAKYL AND LOWER ALKOXY, R2 CAN BE SELECTED FROM LOWER ALKYL, LOWER ALKOXY AND LOWER THIOALKYL. THE COMPOUNDS ARE USEFUL FUNGICIDES AND BIOCIDES.

United States Patent 3,808,252 PHOSPHORYLATED THIOUREA COMPOSITIONS Alexander Mihailovski, Berkeley, and Don R. Baker,

Orinda, Califi, assignors to Stauffer Chemical Company, New York, NY.

No Drawing. Original application Dec. 29, 1971, Ser. No. 213,714. Divided and this application Feb. 26, 1973, Ser. No. 335,606

Int. Cl. C07c 157/00 US. Cl. 260-455 P 3 Claims ABSTRACT OF THE DISCLOSURE New compounds corresponding to the generic formula:

X R NHi Ri wherein X can be selected from oxygen and sulfur, R and R; can be the same or different and can be selected from lower alkyl and lower alkoxy, R can be selected from lower alkyl, lower alkoxy and lower thioalkyl. The compounds are useful fungicides and biocides.

This is a division of application Ser. No. 213,714, filed Dec. 29, 1971.

DESCRIPTION OF THE INVENTION This invention is directed to a novel group of compounds which may be generally described as phosphorylated thioureas which are highly active fungicides and biocides. The compounds of the present invention are represented by the generic formula:

wherein X can be selected from oxygen and sulfur, R and R can be the same or different and can be selected from lower alkyl and lower alkoxy, R can be selected from lower alkyl, lower alkoxy and lower thioalkyl.

The above compounds can. be prepared by phosphorylating o-phenylenediamine on one amino group, followed by treatment of the resulting phosphorylated aniline with a carbonyl isothiocyanate in an inert solvent such as acetone, benzene and the like. The products form rapidly and can be isolated in good purity from the solvent system.

In order to illustrate the merits of the present invention the following examples are provided.

EXAMPLE 1 Preparation of 2-[3'-(methoxycarbonyl)-thioureido]- 0,0-diethylphosphoranilide perature. The resulting chloroform solution was washed twice with 100 ml. portions of water, dried and the solvent evaporated to give crude N-(2-aminophenyl)-0,0-

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diethylphosphoramidate. Upon recrystallization from carbon tetrachloride, 32.5 grams of this product were obtained. Then, 4.6 grams (0.019 mole) N-(Z-aminophenyl)-0,0-diethylphosphoramidate was dissolved in 30 ml. benzene. To this solution was added slowly 2.2 grams (0.019 mole) methoxycarbonyl isothiocyanate dissolved in 10 ml. benzene. The reaction mixture was stirred for about 16 hours at room temperature. A colorless precipitate formed. The solid was filtered and dried to yield 4.6 grams of 2 [3 (methoxycarbonyl)-thioureido]-0,0-diethylphosphorylanilide, M.P. 154-155" C. (dec.). Yield, 67% of theory.

EXAMPLE 2 Preparation of 2-[3'-(methoxycarbonyl)-thioureido]- v O-ethyl-P-ethylthiophosphonanilide N (2 aminophenyl) O-ethyl-P-ethylthiophosphonamidate was prepared from o-phenylenediamine and O ethyl P ethylthiophosphonochloridate under conditions similar to those described for N-(2-aminophenyl)0,0-diethylphosphoramidate in Example 1. To 5.0 grams (0.020 mole) N-(2-aminophenyl)-O-ethyl-P-ethylthiophosphonamidate in 20 ml. benzene was added a solution of 2.4 grams (0.020 mole) methoxycarbonyl isothiocyanate dissolved in 10 ml. benzene. The precipitated solid was filtered and dried to yield 5.6 grams of 2-[3'-(methoxycarbonyl) thioureido] O ethyl-P-ethylthiophosphonanilide, M.P. 172173 C. (dec.). Yield, 76% of theory.

Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above. The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

3 :4- TABLE I-COIlllllllGd Tube test I I 06151 n I m h H w H H A l (1) Bean rust.The chemicals are dissolved in an ap {fi X R R1 R propriate solvent and diluted with tap water to a series of descending concentrations beginning at 50 p.p.m. Sixty OCH2CH3 flOCHiCHJ ml. of each concentration are placed in a test tube. A 3 pinto bean plant is placed in each'tube and supported cm with a piece of cotton so that only the roots and lower 24 S CH3 stem are in contact with the test solution. Forty-eight hours later the bean leaves are inoculated with a water 1O suspension of spores of thebean rust fungus and placed OH; in an environment with 100% humidity for 24 hours. The

FUNGICIDE TESTING PROCEDURES (A) Foliar preventative sprays (1) Bean rust-The chemicals are dissolved in an appropriate solvent and diluted with water containing several drops of Tween 20, a wetting agent. Test concentrations, ranging from 1000 p.p.m. downward, are sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulgaris L.). After the leaves are dried, they are inoculated with a water suspension of. spores of the bean rust fungus (Uromyces phaseoli Arthur) and the plants are placed in an environment of 100% humidity for 24. hours. The plants are then removed from the humidity chamber and held until disease pustules appear on the leaves. Effectiveness is recorded as the lowest concentration, in p.p.m., which will provide 50% reduction in pustule formation as compared to untreated, inoculated plants.

(2) Bean powdery mildew-Test chemicals are prepared and applied in the same manner as for the bean rust test. After the plants are dry, the leaves are dusted with spores of the powdery mildew fungus (Eryspihe polygoni De Candolle) and the plants are retained in the greenhouse until the fungal growth appears on the leaf surface. Effectiveness is recorded as the lowest concentration, in p.p.m., which will provide 50% reduction in pustule formation as compared to untreated, inoculated lants.

P (3) Tomato early blight.Test chemicals are prepared and applied in the same manner as the bean rust and powdery mildew tests except that 4-week old tomato (Lycopersicon esculentum) plants are utilized as the host plant. When the leaves are dry, they are inoculated with a water suspension of spores of the early blight fungus (Alternaris solani Ellis and Martin) and placed in an environment of 100% humidity for 48 hours. The plants are then removed from the humidity chamber and held until disease lesions appear on the leavesu-Eifectiveness is recorded as the lowest concentration, in'p.p.m., which will provide 50% reduction in number of lesions formed as compared to untreated, inoculated plants.

Compound N0.

plants are then removed from the humidity chamber and maintained in the greenhouse until the disease pustules appear on the leaves. Effectiveness is recorded as the lowest concentration, in p.p.m., which will provide reduction in pustule formation as compared to untreated, inoculated plants. I

(2) Bean powdery mildew.-Test chemicals are prepared and applied in the same manner as for the bean rust systemic test. After two days the leaves are dusted with spores of the powdery mildew fungus and maintained in greenhouse until mycelial growth appears on the leaf surfaces. Effectiveness is recorded as the lowest concentration, in p.p.m., which will provide a 50% reduction inmycelial growth on the leaf surface as compared to untreated, inoculated plants. A

(C) Systemic soil drench (1) Bean rust-Pinto beans are grown in l-pint ice cream cartons, each containing 1 lb. of soil. Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted with 25 ml. of water and drenched onto the soil surface. Two days later the bean leaves are inoculated with a water suspension of spores of the rust fungus, and the plants are placed in an environment with humidity for '24 hours. The plants are then removed from the humidity chamber and maintained in the greenhouse until the pustules appear on the leaves. Effectiveness is recorded as the minimum concentration, in p.p.infper lb. of soil,which will provide 50% reduction in number of pustules as compared to untreated inoculated plants.

(2) Bean powdery mildew-The bean plants and chemicals are prepared and applied as in the rust systemic soil drench test. After ten days, the bean leaves are dusted with spores of the powdery mildew fungus and maintained in the'greenhouse until the mycelial growth appears on the leaf surface. Effectiveness is'recorded as the minimum concentration, in p.p.m. per lb.'of soil, which will provide 50% reduction in mycelial gr'owthon the leaf surface in comparison to untreated, inoculated plants.

The results of these tests are tabulated in Table H.

TABLE II Foliar spray Tube systemic Soil drench Rust Mildew Tomato blight Mildew Rust Mildew BIOCIDE TESTING PROCEDURES Tubes of sterilized nutrient and malt extract broth are prepared. Aliquots of the toxicant, dissolved in an appropriate solvent, are injected through the stopper, into the broth, to provide concentrations rangin from 50 ppm. downward. The test organisms consist of two fungi, Aspergillus niger (A.n.) Van Tieghem and Penicillium italicum (P.i.) Wehmer, and two bacteria, Escherichia coli (E.c.) Migula and Staphylococcus aureus (S.a.) Rosenbach. Three drops of a spore suspension of each of the fungi are injected into the tubes of malt broth and three drops of the bacteria are injected into the nutrient broth. One week later the growth of each organism is observed and eflectiveness of the chemical is recorded as the lowest concentration in p.p.m. which provides 50% inhibition of growth as compared to untreated inoculated tubes. The results of these tests are tabulated in Table III.

NOTE )=partial control.

The compounds of this invention are generally embodied into a storm suitable for convenient application. For example, the compounds can be embodied into pesticidal compositions which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays, propellants, such as dichlorodifiuoromethane, etc. If desired, however, the active compounds can be applied directly to feedstulfs, seeds, etc. upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0% by weight of the active pesticide compound.

What is claimed is:

1. Compounds corresponding to the generic formula:

3,749,748 8/1973 Gutman 260--455P ELBERT L. ROBERTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner 

